EP3627604B1 - Membrane de séparation échangeuse d'ions et batterie à circulation la comprenant - Google Patents
Membrane de séparation échangeuse d'ions et batterie à circulation la comprenant Download PDFInfo
- Publication number
- EP3627604B1 EP3627604B1 EP19802759.1A EP19802759A EP3627604B1 EP 3627604 B1 EP3627604 B1 EP 3627604B1 EP 19802759 A EP19802759 A EP 19802759A EP 3627604 B1 EP3627604 B1 EP 3627604B1
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- EP
- European Patent Office
- Prior art keywords
- ion exchange
- exchange resin
- resin layer
- equal
- mol
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Links
- 239000012528 membrane Substances 0.000 title description 14
- 238000005342 ion exchange Methods 0.000 title 1
- 238000000926 separation method Methods 0.000 title 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 142
- 239000003456 ion exchange resin Substances 0.000 claims description 142
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 142
- 239000003014 ion exchange membrane Substances 0.000 claims description 54
- 229920000554 ionomer Polymers 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000012086 standard solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 135
- 239000003792 electrolyte Substances 0.000 description 44
- 239000007788 liquid Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 36
- 229910001456 vanadium ion Inorganic materials 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 230000010220 ion permeability Effects 0.000 description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910052720 vanadium Inorganic materials 0.000 description 12
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 150000003460 sulfonic acids Chemical class 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920003937 Aquivion® Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- a lithium ion battery As a large-capacity power storage system, a lithium ion battery, a sodium sulfur battery, a redox flow battery, an ultra-high capacity capacitor, a lead acid battery and the like have been developed, and among these, a redox flow battery (RFB) has attracted attention as a high capacity and high efficiency secondary battery most suitable for large-sized systems.
- RFB redox flow battery
- such a redox flow battery is a battery using ions in an aqueous solution state as an active material instead of a solid state, and having a mechanism of storing energy by a redox reaction of each of the ions in a positive electrode and a negative electrode.
- Types such as V/Br, Zn/Br and V/V may be included depending on the redox couple, and among these, a vanadium redox flow battery (VRFB) have been more extensively studied compared to other redox flow battery types since it may use the same type of redox material in a cathode and an anode as well as having a high open-circuit voltage.
- VRFB vanadium redox flow battery
- a vanadium redox flow battery uses an electrolyte liquid as a carrier medium, and therefore, an ion exchange membrane is required, and the ion exchange membrane is a key material determining lifetime and manufacturing cost of the vanadium redox flow battery.
- the ion exchange membrane In order to be actually applied to a system using a strong acid material including a transition metal as an electrolyte liquid, the ion exchange membrane needs to have excellent acid resistance and oxidation resistance, and low permeability and excellent mechanical properties are required.
- the ion exchange membrane prevents vanadium ions (V 4+ and V 5+ ) of a positive electrode electrolyte liquid from being crossed over to a negative electrode electrolyte liquid, or vanadium ions (V 2+ and V 3+ ) of a negative electrode electrolyte liquid from being crossed over to a positive electrode electrolyte liquid.
- vanadium ions V 4+ and V 5+
- vanadium ions V 2+ and V 3+
- US 2007/128425 A1 relates to an ion-conductive membrane that includes a first layer comprising a first ionomer, and a porous polymer substrate, where at least a portion of the first ionomer is interpenetrated within the porous polymer substrate by ionomer-induced phase separation.
- JP 2013 168 365 A describes an electrolyte membrane for a redox flow secondary battery that contains a fluorine-based polyelectrolyte polymer with a specific structure.
- the electrolyte membrane has a multilayer structure including three or more layers, and the equilibrium moisture content of the outer layers adjacent to a positive electrode or a negative electrode is higher than the equilibrium moisture content of the intermediate layer that is not adjacent to the positive electrode or the negative electrode.
- the present specification is directed to providing an ion exchange membrane, and a flow battery including the same.
- Another embodiment of the present specification provides a flow battery including a negative electrode; a positive electrode; and the ion exchange membrane as defined in any one of claims 1 to 4 provided between the negative electrode and the positive electrode.
- An ion exchange membrane according to one embodiment of the present specification is capable of enhancing battery performance by effectively preventing a positive electrode electrolyte liquid and a negative electrode electrolyte liquid from being crossed over to each other.
- the ion exchange membrane according to one embodiment of the present specification has high hydrogen ion permeability during charge and discharge, and is thereby capable of enhancing battery performance.
- a redox flow battery is a battery using ions in an aqueous solution state as an active material instead of a solid state, and having a mechanism of storing energy by a redox reaction of each of the ions in a positive electrode and a negative electrode.
- Types such as V/Br, Zn/Br and V/V may be included depending on the redox couple, and among these, a vanadium redox flow battery (VRFB) have been more extensively studied compared to other redox flow battery types since it may use the same type of redox material in a cathode and an anode as well as having a high open-circuit voltage.
- VRFB vanadium redox flow battery
- a vanadium redox flow battery uses an electrolyte liquid as a carrier medium, and therefore, an ion exchange membrane is required, and the ion exchange membrane is a key material determining lifetime and manufacturing cost of the vanadium redox flow battery.
- the ion exchange membrane In order to be actually applied to a system using a strong acid material including a transition metal as an electrolyte liquid, the ion exchange membrane needs to have excellent acid resistance and oxidation resistance, and low permeability and excellent mechanical properties are required.
- the ion exchange membrane prevents vanadium ions (V 4+ and V 5+ ) of a positive electrode electrolyte liquid from being crossed over to a negative electrode electrolyte liquid, or vanadium ions (V 2+ and V 3+ ) of a negative electrode electrolyte liquid from being crossed over to a positive electrode electrolyte liquid.
- vanadium ions V 4+ and V 5+
- vanadium ions V 2+ and V 3+
- the ion exchange membrane according to the present specification is capable of enhancing battery performance by effectively preventing a positive electrode electrolyte liquid and a negative electrode electrolyte liquid from being crossed over to each other.
- crossover of vanadium ions may be effectively prevented while increasing hydrogen ion conductivity.
- the ion exchange membrane according to the present specification as defined in claim 1 has high hydrogen ion permeability during charge and discharge, and therefore, battery performance may be enhanced.
- the ion exchange membrane according to the present specification being provided with a multilayered ion exchange resin layer, an effect of preventing a crossover of vanadium ions while increasing hydrogen ion conductivity may be obtained.
- the ion exchange membrane according to the present specification being provided with second and third ion exchange resin layers including ionomers having a higher EW than an ionomer of a first ion exchange resin layer on both surfaces of the first ion exchange resin layer, a crossover may be effectively prevented compared to an asymmetric form having a layer provided on only one surface of a first ion exchange resin layer.
- a crossover occurring on a surface opposite to the surface provided with the second ion exchange resin layer may not be prevented.
- the EW equivalent weight
- the unit is g/mol or g/eq.
- the EW may be obtained by calculating the number of moles of sulfonic acid per 1 g through titration. For example, a polymer corresponding to 1 g is introduced to 3 M NaCl, and after stirring the result for 1 day, a 0.1 M NaOH standard solution is added until the pH becomes 7, and the EW may be calculated through the following Equation 1.
- EW g mol m NaOH ⁇ V NaOH ⁇ 1000
- the first to the third ion exchange resin layers each have a thickness of preferably greater than or equal to 5 ⁇ m and less than or equal to 30 ⁇ m, more preferably 5 ⁇ m to 25 ⁇ m, and most preferably 7 ⁇ m to 20 ⁇ m.
- energy efficiency decreases.
- the thickness of the first ion exchange resin layer is less than 5 ⁇ m, an effect of enhancing hydrogen ion conductivity is not high, and the thickness being greater than 30 ⁇ m has a disadvantage in that it is difficult to identify effects of other layers.
- the ion exchange membrane includes a fourth ion exchange resin layer provided on a surface opposite to the surface in contact with the first ion exchange resin layer of the second ion exchange resin layer, and a fifth ion exchange resin layer provided on a surface opposite to the surface in contact with the first ion exchange resin layer of the third ion exchange resin layer.
- the fourth ion exchange resin layer and the fifth ion exchange resin layer each include one or more types of ionomers.
- the first ion exchange resin layer (101) includes one or more types of ionomers having an equivalent weight EW of greater than or equal to 500 g/mol and less than or equal to 750 g/mol; the second ion exchange resin layer (102) and the third ion exchange resin layer (103) each include one or more types of ionomers having an equivalent weight EW of greater than 750 g/mol and less than or equal to 900 g/mol; and the fourth ion exchange resin layer (104) and the fifth ion exchange resin layer (105) each include one or more types of ionomers having an equivalent weight EW of greater than 900 g/mol and less than or equal to 1,100 g/mol, and the ionomer included in each of the fourth ion exchange resin layer and the fifth ion exchange resin layer has a higher EW than the ionomers of the second ion exchange resin layer and the third ion exchange resin layer.
- FIG. 1 illustrates an example of the ion exchange membrane according to an embodiment of the present specification.
- a structure of the ion exchange membrane having a third ion exchange resin layer (103) provided on a fifth ion exchange resin layer (105), a first ion exchange resin layer (101) provided on the third ion exchange resin layer, a second ion exchange resin layer (102) provided on the first ion exchange resin layer, and a fourth ion exchange resin layer (104) provided on the second ion exchange resin layer is illustrated.
- the first ion exchange resin layer includes one or more types of ionomers having an EW of greater than or equal to 500 g/mol and less than or equal to 750 g/mol, preferably greater than or equal to 650 g/mol and less than or equal to 720 g/mol, and more preferably greater than or equal to 700 g/mol and less than or equal to 720 g/mol, and
- the second ion exchange resin layer and the third ion exchange resin layer each include one or more types of ionomers having an EW of greater than 750 g/mol and less than or equal to 900 g/mol, preferably greater than or equal to 790 g/mol and less than or equal to 870 g/mol, and more preferably greater than or equal to 790 g/mol and less than or equal to 830 g/mol
- the fourth ion exchange resin layer and the fifth ion exchange resin layer each include one or more types of ionomers having an EW of greater than 900 g/mol and less than or equal to 1,100 g/mol, preferably greater than 900 g/mol and less than or equal to 1000 g/mol, and more preferably greater than or equal to 930 g/mol and less than or equal to 980 g/mol.
- the thicknesses of the fourth ion exchange resin layer and the fifth ion exchange resin layer are the same as or different from each other, and each preferably greater than or equal to 5 ⁇ m and less than or equal to 30 ⁇ m, more preferably from 5 ⁇ m to 20 ⁇ m, and most preferably from 7 ⁇ m to 15 ⁇ m.
- each of the ion exchange resin layers may be adjusted during a process of coating the ion exchange membrane.
- the thickness of the formed separator varies depending on the height difference between the bar and the bottom, and the thickness of the ion exchange resin layer may be adjusted therethrough.
- the ion exchange membrane may include a multilayer structure in which the outer layer is an ion exchange resin layer including an ionomer having the highest EW in the same manner as described above.
- the ion exchange membrane includes a sixth ion exchange resin layer provided on a surface opposite to the surface in contact with the second ion exchange resin layer of the fourth ion exchange resin layer, and a seventh ion exchange resin layer provided on a surface opposite to the surface in contact with the third ion exchange resin layer of the fifth ion exchange resin layer,
- FIG. 2 illustrates an example of the ion exchange membrane according to still another embodiment of the present specification.
- a structure of the ion exchange membrane having a fifth ion exchange resin layer (105) provided on a seventh ion exchange resin layer (107), a third ion exchange resin layer (103) provided on the fifth ion exchange resin layer, a first ion exchange resin layer (101) provided on the third ion exchange resin layer, a second ion exchange resin layer (102) provided on the first ion exchange resin layer, a fourth ion exchange resin layer (104) provided on the second ion exchange resin layer, and a sixth ion exchange resin layer provided on the fourth ion exchange resin layer is illustrated.
- the sixth to the seventh ion exchange resin layers each include one or more types of ionomers having an EW of greater than or equal to 500 g/mol and less than or equal to 1,100 g/mol, and includes one or more types of ionomers having an EW of preferably greater than or equal to 700 g/mol and less than or equal to 1,000 g/mol, and more preferably greater than or equal to 720 g/mol and less than or equal to 980 g/mol.
- the thicknesses of the sixth ion exchange resin layer and the seventh ion exchange resin layer are the same as or different from each other, and each preferably greater than or equal to 5 ⁇ m and less than or equal to 30 ⁇ m, more preferably from 5 ⁇ m to 20 ⁇ m, and most preferably from 7 ⁇ m to 15 ⁇ m.
- the ion exchange membrane preferably has a thickness of greater than or equal to 15 ⁇ m and less than or equal to 200 ⁇ m, more preferably greater than or equal to 20 ⁇ m and less than or equal to 100 ⁇ m, and most preferably greater than or equal to 20 ⁇ m and less than or equal to 50 ⁇ m. Specifically, when the ion exchange membrane has a thickness of greater than or equal to 20 ⁇ m and less than or equal to 50 ⁇ m, highest efficiency is obtained.
- One embodiment of the present specification provides a flow battery including a negative electrode; a positive electrode; and the ion exchange membrane provided between the negative electrode and the positive electrode.
- the flow battery of the present specification may be formed with a negative electrode tank (anolyte tank) and a positive electrode tank (catholyte tank) respectively storing a negative electrode electrolyte liquid or a positive electrode electrolyte liquid; pumps each connected to the negative electrode tank and the positive electrode tank to supply the electrolyte liquid to a negative electrode and a positive electrode; a positive electrode cell (positive half-cell) and a negative electrode cell (negative half-cell) in which vanadium ions, an active material in the electrolyte liquid, are oxidized and reduced; and the ion exchange membrane provided between the positive electrode cell and the negative electrode cell.
- FIG. 3 illustrates the flow battery of the present specification, and the flow battery is not limited thereto.
- the positive electrode means an electrode reduced by receiving electrons when discharged, and, on the contrary, may perform a role of a negative electrode (oxidation electrode) exporting electrons when charging a battery by a positive electrode active material being oxidized.
- oxidation electrode oxidation electrode
- the negative electrode means an electrode exporting electrons by being oxidized when discharged, and, on the contrary, may perform a role of a positive electrode (reduction electrode) reduced by receiving electrons when charging a battery.
- the positive electrode and the negative electrode each include a current collector; and porous carbon such as carbon felt provided between the current collector and the membrane, and the positive electrode means a region capable of charging and discharging electric energy by the positive electrode electrolyte liquid reacting while being injected and discharged from the positive electrode tank, and the negative electrode means a region capable of charging and discharging electric energy by the negative electrode electrolyte liquid reacting while being injected and discharged from the negative electrode tank.
- the positive electrode electrolyte liquid and the negative electrode electrolyte liquid may respectively include a positive electrode active material and a negative electrode active material as an electrolyte liquid active material.
- the positive electrode active material means a material reduced by receiving electrons when discharged and exporting electrons by being oxidized when charged
- the negative electrode active material means a material exporting electrons by being oxidized when discharged and reduced by receiving electrons when charged.
- the positive electrode electrolyte liquid may include at least one of V 5+ and V 4+
- the negative electrode electrolyte liquid may include at least one of V 2+ and V3 + .
- the positive electrode electrolyte liquid and the negative electrode electrolyte liquid may further include a solvent, and the solvent is not particularly limited as long as it is capable of dissolving the electrolyte liquid active material, and examples thereof may include an aqueous sulfuric acid solution, an aqueous hydrochloric acid solution, an aqueous nitric acid solution and a mixed solution thereof.
- a molar concentration of the acid in the aqueous sulfuric acid solution, the aqueous hydrochloric acid solution, the aqueous nitric acid solution or a mixed solution thereof may be greater than or equal to 1 M and less than or equal to 6 M.
- a molar number of the acid in 1 liter of the electrolyte liquid may be greater than or equal to 1 mol and less than or equal to 6 mol.
- the acid means sulfuric acid, hydrochloric acid, nitric acid or a mixture thereof
- the aqueous sulfuric acid solution, the aqueous hydrochloric acid solution, the aqueous nitric acid solution or a mixed solution thereof refers to respectively adding sulfuric acid, hydrochloric acid, nitric acid or a mixture thereof to water.
- the flow battery may be a vanadium flow battery.
- the flow battery may be a vanadium flow battery in which the positive electrode electrolyte liquid includes at least one of V 5+ and V 4+ , and the negative electrode electrolyte liquid includes at least one of V 2+ and V 3+ .
- One embodiment of the present specification provides a battery module including the flow battery as a unit cell.
- the battery module may be formed by inserting a bipolar plate between the flow batteries of the present specification and staking the result.
- the battery module may specifically be used as a power supply of electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles or power storage systems.
- An AquivionE98 solution was formed as a film using a 100 ⁇ m thickness coating bar to form a third ion exchange resin layer.
- an AquivionE72 solution was formed as a film using a 200 ⁇ m thickness coating bar to form a first ion exchange resin layer.
- An AquivionE98 solution was formed as a film thereon using a 300 ⁇ m thickness coating bar to form a second ion exchange resin layer.
- the result was dried for 3 hours at 80°C, 15 hours at 180°C and 4 minutes at 200°C, and then dipped in distilled water for swelling to prepare ion exchange membrane 1 having each layer thickness as in the following Table 1.
- Table 1 Layer Thickness ( ⁇ m) Second Ion Exchange Resin Layer 15 First Ion Exchange Resin Layer 20 Third Ion Exchange Resin Layer 15 Ion Exchange Membrane 1 (Final) 50
- An AquivionE98 solution was formed as a film using a 50 ⁇ m thickness coating bar to form a fifth ion exchange resin layer.
- an AquivionE83 solution was formed as a film using a 100 ⁇ m thickness coating bar to form a third ion exchange resin layer.
- An AquivionE72 solution was formed as a film thereon using a 150 ⁇ m thickness coating bar to form a first ion exchange resin layer.
- An AquivionE83 solution was formed as a film thereon using a 200 ⁇ m thickness coating bar to form a second ion exchange resin layer.
- an AquivionE98 solution was formed as a film using a 250 ⁇ m thickness coating bar to form a fourth ion exchange resin layer.
- An AquivionE98 solution was formed as a film using a 300 ⁇ m thickness coating bar to form a single layer ion exchange resin layer. After that, in a circulating oven, the result was dried under the same condition as in Reference Example 1, and then dipped in distilled water for swelling to prepare ion exchange membrane A having a thickness of 50 ⁇ m.
- An AquivionE72 solution was formed as a film using a 300 ⁇ m thickness coating bar to form a single layer ion exchange resin layer. After that, in a circulating oven, the result was dried under the same condition as in Reference Example 1, and then dipped in distilled water for swelling to prepare ion exchange membrane B having a thickness of 50 ⁇ m.
- An AquivionE98 solution and an AquivionE72 solution were mixed in a weight ratio of 65:35 to prepare an ionomer solution having an EW of 870 g/mol. This was formed as a film using a 300 ⁇ m thickness coating bar to form a single layer ion exchange resin layer. After that, in a circulating oven, the result was dried under the same condition as in Reference Example 1, and then dipped in distilled water for swelling to prepare ion exchange membrane C having a thickness of 50 ⁇ m.
- An AquivionE72 solution was formed as a film using a 100 ⁇ m thickness coating bar to form a first ion exchange resin layer.
- an ionomer solution Nafion manufactured by Dupont (25 wt% in water/isopropanol) having an EW of 1,100 g/mol was formed as a film using a 300 ⁇ m thickness coating bar to form a second ion exchange resin layer.
- the result was dried under the same condition as in Reference Example 1, and then dipped in distilled water for swelling to prepare ion exchange membrane D having each layer thickness as in the following Table 3.
- Table 3 Layer Thickness ( ⁇ m) Second Ion Exchange Resin Layer 15 First Ion Exchange Resin Layer 35 Ion Exchange Membrane D (Final) 50
- An AquivionE72 solution was formed as a film using a 100 ⁇ m thickness coating bar to form a third ion exchange resin layer. Thereon, an AquivionE98 solution was formed as a film thereon using a 200 ⁇ m thickness coating bar to form a first ion exchange resin layer. An AquivionE72 solution was formed as a film thereon using a 300 ⁇ m thickness coating bar to form a second ion exchange resin layer. After that, in a circulating oven, the result was dried under the same condition as in Reference Example 1, and then dipped in distilled water for swelling to prepare ion exchange membrane E having each layer thickness as in the following Table 4. [Table 4] Layer Thickness ( ⁇ m) Second Ion Exchange Resin Layer 15 First Ion Exchange Resin Layer 20 Third Ion Exchange Resin Layer 15 Ion Exchange Membrane E (Final) 50
- carbon felt was installed on a unit cell having an active area of 25 cm 2 as an electrode and each of the membranes of the examples and the comparative examples was installed, and as an electrolyte liquid, vanadium 1.6 M, sulfuric acid 2 M aqueous solution (manufacturer: OXKEM) was used.
- the electrolyte liquid (50 mL each) was supplied through circulation at a rate of 1 mL/min.cm 2 , and with a current of 200 mA/cm 2 , charging to 1.7 V and discharging to 0.8 V was repeated 50 times.
- residual capacity represents capacity of the battery after conducting the charge and discharge test 50 times
- average efficiency of 20 times represents an average value of current, voltage and energy efficiency measured for the first 20 times.
- the energy efficiency represents, after measuring each energy during charge/discharge, an energy value during discharge with respect to energy during charge as a percentage.
- the average EW is a value obtained by multiplying the EW value of the ionomer used in each layer by the thickness of each layer, and dividing the product by the total thickness.
- FIGs. 4 to 7 are graphs presenting residual capacity, current efficiency, voltage efficiency and energy efficiency for each of the single cells of Reference Example 1 and Comparative Examples 1 to 3 depending on the number of charge and discharge. Specifically, residual capacity of FIG. 4 presents the ratio when employing 100% as 1.0.
- Residual capacity of FIG. 8 shows the ratio when employing 100% as 1.0 with respect to residual capacity up to 20 times of the charge and discharge test.
- Reference Example 1 maintained the same level of current efficiency while having a smaller residual capacity decrease rate.
- FIGs. 10 and 11 are photographs of the appearances of the membranes prepared in Comparative Examples 4 and 5, respectively, and it was identified that, in Comparative Example 4, the membrane was curled when dipped in water since the degree of swelling on both sides was different when wetted due to the asymmetric structure. In this case, workability becomes inferior making it difficult to tighten a battery. Meanwhile, it was identified that, in Comparative Example 5, the membrane was not curled since it has a symmetric structure regardless of the EW value.
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Claims (5)
- Membrane d'échange d'ions comprenant :une première couche de résine d'échange d'ions (101) ; etune deuxième couche de résine d'échange d'ions (102) et une troisième couche de résine d'échange d'ions (103) respectivement prévues sur les deux surfaces de la première couche de résine d'échange d'ions (101),une quatrième couche de résine d'échange d'ions (104) prévue sur une surface à l'opposé de la surface en contact avec la première couche de résine d'échange d'ions (101) de la deuxième couche de résine d'échange d'ions (102) ; etune cinquième couche de résine d'échange d'ions (105) prévue sur une surface à l'opposé de la surface en contact avec la première couche de résine d'échange d'ions (101) de la troisième couche de résine d'échange d'ions (103),dans laquelle les première à cinquième couches de résine d'échange d'ions (101, 102, 103, 104, 105) incluent chacune un ou plusieurs types d'ionomères ;l'ionomère inclus dans chacune parmi la deuxième couche de résine d'échange d'ions (102) et la troisième couche de résine d'échange d'ions (103) présente un poids équivalent supérieur à celui de l'ionomère de la première couche de résine d'échange d'ions (101) ; etl'ionomère inclus dans chacune parmi la quatrième couche de résine d'échange d'ions (104) et la cinquième couche de résine d'échange d'ions (105) présente un poids équivalent supérieur à celui des ionomères de la deuxième couche de résine d'échange d'ions (102) et de la troisième couche de résine d'échange d'ions (103) ;dans laquelle la première couche de résine d'échange d'ions (101) inclut un ou plusieurs types d'ionomères présentant un poids équivalent supérieur ou égal à 500 g/mol et inférieur ou égal à 750 g/mol ;la deuxième couche de résine d'échange d'ions (102) et la troisième couche de résine d'échange d'ions (103) incluent chacune un ou plusieurs types d'ionomères présentant un poids équivalent supérieur ou égal à 750 g/mol et inférieur ou égal à 900 g/mol ; etla quatrième couche de résine d'échange d'ions (104) et la cinquième couche de résine d'échange d'ions (105) incluent chacune un ou plusieurs types d'ionomères présentant un poids équivalent supérieur ou égal à 900 g/mol et inférieur ou égal à 1100 g/mol,dans laquelle le poids équivalent (EW) signifie un poids d'un polymère ayant 1 équivalent d'acide sulfonique et est déterminé comme suit :un polymère correspondant à 1 g est introduit dans 3 M de NaCl et, après l'agitation du résultat pendant 1 jour, une solution étalon de 0,1 M de NaOH est ajoutée jusqu'à ce que le pH devienne 7 ; et le poids équivalent (EW) est calculé selon l'équation suivantedans laquelle *m=masse de polymère=1 g, *[NaOH]=0,1 M et *VNaOH=volume de NaOH introduit.
- Membrane d'échange d'ions selon la revendication 1, dans laquelle les première à troisième couches de résine d'échange d'ions (101, 102, 103) présentent chacune une épaisseur supérieure ou égale à 5 µm et inférieure ou égale à 30 µm.
- Membrane d'échange d'ions selon la revendication 1, dans laquelle les première à cinquième couches de résine d'échange d'ions (101, 102, 103, 104, 105) présentent chacune une épaisseur supérieure ou égale à 5 µm et inférieure ou égale à 30 µm.
- Membrane d'échange d'ions selon la revendication 1, dans laquelle la membrane d'échange d'ions présente une épaisseur supérieure ou égale à 15 µm et inférieure ou égale à 200 µm.
- Batterie à flux comprenant :une électrode négative ;une électrode positive ; etla membrane d'échange d'ions selon l'une quelconque des revendications 1 à 4 prévue entre l'électrode négative et l'électrode positive.
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PCT/KR2019/003931 WO2019221387A1 (fr) | 2018-05-17 | 2019-04-03 | Membrane de séparation échangeuse d'ions et batterie à circulation la comprenant |
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JP2006059756A (ja) * | 2004-08-23 | 2006-03-02 | Toyota Motor Corp | 固体高分子電解質膜及びこれを用いた固体高分子型燃料電池、並びに、これらの製造方法 |
JP4841195B2 (ja) * | 2005-08-05 | 2011-12-21 | 旭化成株式会社 | 燃料電池用電解質膜 |
US20070128425A1 (en) * | 2005-12-07 | 2007-06-07 | 3M Innovative Properties Company | Reinforced ion-conductive membranes |
WO2010067743A1 (fr) * | 2008-12-12 | 2010-06-17 | 株式会社クラレ | Membrane électrolytique multicouches, ensemble électrode-membrane et pile à combustible |
US20120045704A1 (en) * | 2010-08-18 | 2012-02-23 | E.I. Du Pont De Nemours And Company | Durable ionomeric polymer for proton exchange membrane and membrane electrode assemblies for electrochemical fuel cell applications |
US20120202099A1 (en) * | 2011-02-08 | 2012-08-09 | United Technologies Corporation | Flow battery having a low resistance membrane |
JP6131051B2 (ja) * | 2012-01-20 | 2017-05-17 | 旭化成株式会社 | レドックスフロー二次電池用電解質膜及びそれを用いたレドックスフロー二次電池 |
JP6090971B2 (ja) * | 2012-06-19 | 2017-03-08 | 株式会社カネカ | 高分子電解質膜、およびその利用 |
WO2014099874A1 (fr) | 2012-12-17 | 2014-06-26 | E. I. Du Pont De Nemours And Company | Batterie à circulation pourvue d'une membrane de séparation comprenant un ionomère |
JP6034200B2 (ja) | 2013-01-08 | 2016-11-30 | 旭化成株式会社 | レドックスフロー二次電池 |
KR20180100457A (ko) | 2013-05-16 | 2018-09-10 | 유나이티드 테크놀로지스 코포레이션 | 최대 물 영역 클러스터 크기를 갖는 수화 이온-교환막을 갖는 흐름 전지 |
KR20150062496A (ko) | 2013-11-29 | 2015-06-08 | 주식회사 엘지화학 | 분리막, 이를 포함하는 전기화학 전지 및 분리막의 제조방법 |
EP3200258B1 (fr) * | 2014-09-23 | 2020-11-04 | LG Chem, Ltd. | Membrane composite contenant un polymère de transfert d'ions et son procédé de préparation |
KR20170069783A (ko) * | 2015-12-11 | 2017-06-21 | 주식회사 엘지화학 | 고분자 전해질 연료전지용 촉매 슬러리 조성물, 막-전극 접합체, 및 막 -전극 접합체의 제조방법 |
US11417904B2 (en) * | 2016-02-03 | 2022-08-16 | Camx Power Llc | Bipolar ionomer membrane |
KR20180056466A (ko) | 2016-11-18 | 2018-05-29 | 주식회사 오윈 | 블랙박스와 결제수단 연계 등록 방법 |
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JP7069224B2 (ja) | 2022-05-17 |
WO2019221387A1 (fr) | 2019-11-21 |
EP3627604A1 (fr) | 2020-03-25 |
US11309567B2 (en) | 2022-04-19 |
KR102248538B1 (ko) | 2021-05-04 |
KR20190131722A (ko) | 2019-11-27 |
JP2020524386A (ja) | 2020-08-13 |
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